Adhesive material composition and method

ABSTRACT

An adhesive material includes a vinyl polymer and a solvent that includes xylene and toluene. The adhesive material has a viscosity in the range from about 1.0 cP to about 20.0 cP such that the adhesive material can be applied to a surface using an ink jet print head.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. Provisional PatentApplication No. 61/903,816, filed Nov. 13, 2013, entitled “Battery”;U.S. Provisional Patent Application No. 61/903,829, filed Nov. 13, 2013,entitled “Adhesive Material Composition and Method”; U.S. ProvisionalPatent Application No. 61/903,819, filed Nov. 13, 2013, entitled“Insulator Material Composition and Method”; U.S. Provisional PatentApplication No. 61/905,697, filed Nov. 18, 2013, entitled “CathodeMaterial Composition and Methods of Preparing and Applying”; U.S.Provisional Patent Application No. 61/903,846, filed Nov. 13, 2013,entitled “Electrolyte Material Composition and Method”; and U.S.Provisional Patent Application No. 61/903,859, filed Nov. 13, 2013,entitled “Lithium Composition and Methods.” The entire contents of allof these applications are incorporated herein by reference.

FIELD OF DISCLOSURE

The present application is directed to a battery, a batterymanufacturing system and method, and more particularly to thin-filmbatteries, and manufacturing systems and methods thereof.

BACKGROUND

Thin-film batteries are used in applications such as smart cards,medical devices, and consumer products. Typically, the thin-film batteryincludes electrode materials disposed on either side of a separator.Tabs or conductive contacts are coupled to the electrode materials, andthe electrode materials and the separator are sealed within an enclosuresuch that conductive contacts extend beyond the enclosure while theelectrode materials and the separator are isolated from the environmentoutside the battery.

SUMMARY

In one embodiment, an adhesive material includes a vinyl polymer and asolvent that includes xylene and toluene. The adhesive material has aviscosity in the range from about 1.0 cP to about 20.0 cP such that theadhesive material can be applied to a surface using an ink jet printhead.

In another embodiment, an adhesive adapted to be applied using an inkjet print head includes from about 1.0% to about 8.0% by weight of avinyl polymer, from about 1.0% to about 99.0% by weight of toluene, andfrom about 1.0% to about 99.0% by weight of xylene, and up to about1.5.0% by weight of a surfactant. The adhesive has a viscosity such thatthe adhesive can be jetted by the ink jet print head.

In a further embodiment, a method of manufacturing a battery using anink jet print head includes the step of jetting an adhesive comprising asolvent onto a surface, and vaporizing a portion of the solvent. Theadhesive material has a viscosity in the range from about 1.0 cP toabout 20.0 cP.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an isometric view of a battery according to the presentdisclosure;

FIG. 2 is a cross-sectional view taken generally along the lines 2-2 ofFIG. 1;

FIG. 3A is a plan view of the interior of the battery of FIG. 1 shownprior to folding and with portions removed;

FIGS. 3B and 3C are cross-sectional views taken generally along thelines 3B-3B of FIG. 3A illustrating alternative embodiments of thebattery of FIG. 1;

FIGS. 4 and 4 a are cross-sectional views taken generally along thelines 4-4 of FIG. 1 of another embodiment of the battery of FIG. 1;

FIGS. 5A through 5E are plan views of the interior of the embodiment ofFIG. 4 and illustrate application of different components of suchembodiment;

FIG. 6A is a plan view of another embodiment of the battery of FIG. 1;

FIG. 6B is a cross-sectional view taken generally along the lines 6B-6Bof FIG. 6A;

FIG. 7 is a plan view of yet another embodiment of the battery of FIG.1;

FIG. 8 is a plan view of an embodiment of a multi-cell battery madeusing the battery of FIG. 1;

FIG. 9 is a plan view of another embodiment of a multi-cell battery madeusing the battery of FIG. 1;

FIG. 10 is an isometric view of another embodiment of a battery;

FIG. 11 is a partially exploded, cross-sectional view taken generallyalong the lines 11-11 of FIG. 10;

FIG. 12 is a block diagram of a manufacturing system that may be used toproduce the battery of FIG. 10;

FIG. 13A is an isometric view of another embodiment of a battery;

FIG. 13B is a sectional view taken generally along the lines 13B-13B ofFIG. 13A;

FIG. 14 is a diagram of a method of preparing an embodiment of a cathodematerial;

FIG. 15 is a diagram of an alternative method of preparing a furtherembodiment of the cathode material; and

FIG. 16 is a schematic illustration of one embodiment of a device usedfor jetting battery materials.

DETAILED DESCRIPTION

Referring to FIG. 1, a battery 100 includes a substrate 102 that has anouter surface (or face) 104. The battery 100 further includes a cathodetab 106 and an anode tab 108 that may be connected to correspondingconnectors of a device to be powered by the battery 100.

Referring to FIGS. 2, 3A, and 3B, an inner surface (or face) 120opposing the outer surface 104 of the substrate 102 includes an outerperimeter 109 that surrounds a first margin region or portion 122 and asecond margin region or portion 124, and an interior region or portion126. An adhesive material 128 is disposed on the inner surface 120, inat least one or both of the first margin region 122 and the secondmargin region 124. In some embodiments, the adhesive material 128 isdisposed such that at least a portion of the interior region 126 of theinner surface 120 is substantially free of the adhesive material 128.

A layer of cathode material 130 is disposed in the interior region 126of the inner surface 120. The cathode tab 106 is disposed such that thecathode tab 106 is conductively coupled to the cathode material 130 andextends outwardly beyond the adhesive material 128 deposited on innersurface 120 of the substrate 102.

In some embodiments, the substrate 102 comprises a conductive materialand the layer of cathode material 130 is disposed such that the layer ofcathode material 130 is conductively coupled to the substrate 102. Forsome applications, the outer surface 104 of the substrate 102 may beconnected to a device powered by the battery 100, and a separate cathodetab 106 may not be necessary. Alternately, the cathode tab 106 may bedisposed on the outer surface 104 of the substrate 102 or the innersurface 120 of the substrate 102, or may be integral to the substrate102. It should be apparent that the cathode tab 106 may be disposed toextend outwardly from any side of the battery 100.

A layer of an electrolyte material 132 is disposed on top of at least aportion of the layer of cathode material 130. A layer of an anodematerial 134 is disposed on top of at least a portion of the layer ofelectrolyte material 132. The layer of cathode material 130, layer ofelectrolyte material 132, and the layer of anode material 134 aredisposed such that the layer of electrolyte material 132 conductivelyseparates the layer of cathode material 130 from the anode material 134,yet allows ionic transfer therebetween.

The anode tab 108 is disposed so that the anode tab 108 is conductivelycoupled with the layer of anode material 134 and extends outwardlybeyond a perimeter 136 of the substrate 102. In some embodiments, theanode tab 108 may be disposed between the layer of anode material 134and the layer of electrolyte material 132 or on top of the layer ofanode material 134, or may be integral to the layer of anode material134.

After the internal components of the battery 100, including the adhesivematerial 128, the layer of cathode material 130, the layer ofelectrolyte material 132, and the layer of anode material 134, aredisposed as described above, the substrate 102 is folded along a line138 to define a fold section or portion 139 so that the adhesivematerial 128 disposed in the first margin region 122 is brought intocontact with the adhesive material 128 in the second margin region 124,forming a folded configuration. In some embodiments, a vacuum isgenerated in the environment surrounding the battery so that any air orother vapors present in the interior of the battery 100 may be evacuatedand the adhesive material 128 is activated to seal the battery 100.

Referring to FIG. 3C, in some embodiments of the battery 100, aninsulating material 144 is disposed in the first margin region 122 andthe second margin region 124. The layer of cathode material 130 isdisposed in, at least, the interior region 126 that does not have theinsulating material 144 disposed therein. The adhesive material 128 isdisposed, at least, on top of the insulating material 144. As shown inFIG. 3C, in some embodiments, the adhesive material 128 may be disposedon top of both the insulating material 144 and a portion 145 of thelayer of the cathode material 130. The layer of electrolyte material 132is disposed on the top of the layer of the cathode material 130. Theanode tab 108 is disposed on top of the adhesive material 128. In someembodiments, the anode tab 108 is disposed such that the anode tab 108is coupled to the electrolyte material 132. The layer of anode material134 is disposed such that the layer of anode material 134 is coupled tothe layer of electrolyte material 132 and the anode tab 108.

With reference to FIGS. 4 and 4A, in some embodiments, the battery 100may be constructed to have a substantially flat profile when viewed fromthe side. Such a flat profile may be achieved by disposing the anode tab108 into a recess (or notch) in the layer of electrolyte material 132.In such embodiments, the anode tab 108 is disposed so that a top surface140 of the anode tab 108 is substantially coplanar with a top surface142 of the layer of electrolyte material 132.

Referring to FIGS. 4 and FIGS. 5A-5E, an insulating material 144 isdisposed directly or indirectly on inner surface 120 of the substrate102 (FIG. 5A). A first portion 146 of the insulating material 144 a anda second portion 148 of the insulating material 144 b are disposedadjacent a first edge 150 and a second edge 152, respectively, of thesubstrate 102. The insulating material 144 is disposed so that when theanode tab 108 is disposed, the insulating material 144 conductivelyisolates the disposed anode tab 108 from substrate 120.

The adhesive material 128 is disposed in at least the first marginregion 122 and the second margin region 124 of the inner surface 120(FIG. 5B). In some embodiments, the adhesive material 128 may bedisposed to cover a portion of one or both of the first portion 146 andthe second portion 148 of the insulating material 144.

The layer of cathode material 130 is disposed in the interior region 126of the inner surface 120 (FIG. 5C). The layer of cathode material 130 isdisposed so that the second portion 148 of the insulating material 144is not covered thereby and so that a top surface 154 of the layer ofcathode material 130 does not extend outwardly beyond a top surface 156of the second portion 148 of the insulating material 144.

The layer of electrolyte material 132 is disposed on top of the layer ofcathode material 130, and the anode tab 108 is disposed on top of thesecond portion 148 of the insulating material 144 (FIG. 4). In someembodiments, some electrolyte material 132 (shown in FIG. 4A) may bedisposed between the anode tab 108 and the second portion 148 of theinsulating material so that the top surface 140 of the anode tab 108 andthe top surface of the layer of electrolyte material 132 aresubstantially coplanar. In some embodiments, the anode tab 108 contactsthe adhesive material 128 disposed on top of portions 146 and 148 of theinsulating material 144 and such adhesive material 128 facilitatessecuring the anode tab 108 to the battery 100.

The layer of anode material 134 is disposed in contact with both thelayer of electrolyte material 132 and the anode tab 108 (FIG. 5E).Although FIG. 5E shows the anode material 134 disposed on one-half ofthe interior region 126 of the inner surface 120, it should be apparentthat the anode material 134 may be disposed on both halves of the innersurface 120 or disposed to be substantially coextensive with the innersurface 120.

Referring to FIGS. 6A and 6B, in some embodiments, the layer of cathodematerial 130 may be disposed on a face of a first half or portion 158and a face of a second half or portion 160 of the interior region 126 sothat there is a gap 162 in the layer of cathode material 130. Similarly,the layer of electrolyte material 132 may be disposed on either side ofthe gap 162. The layer of anode material 134 may be disposed on only oneside of the gap 162 or on either side of the gap 162. As shown in FIGS.6A and 6B, it should be apparent that the first portion 158 and thesecond portion 160 are integral substrate portions. The gap 162 formedin this manner may facilitate folding of the battery 100 after the layerof cathode material 130, the layer of electrolyte material 132, and thelayer of anode material 134 have been disposed.

The substrate 102 may be copper, nickel coated copper, aluminum,carbon-coated aluminum, or other similar material. In some embodimentsthe adhesive material 128 may be a heat-activated adhesive or apressure-activated adhesive, and may be electrically insulative orelectrically conductive. In other embodiments, both pressure and heatmay be used to activate the adhesive material 128. The layer of anodematerial 134 may be, for example, lithium or zinc. Other metals or metalcompositions may be apparent to those in the art that may be used forthe anode material 134. The layer of anode material 134 may be providedas a sheet of material, a powder, and/or a suspension. Appropriatematerials that comprise the layer of cathode materials 130 that arecompatible for use in a battery with a selected anode material 134 willbe apparent to those who have skill in the art. Such materials mayinclude manganese dioxide, titanium dioxide, and lithium dioxide.

Materials appropriate for use for the layer of electrolyte material 132may include one or more of a semi-solid gel, a polymer, and a metal salt(for example, a lithium salt). In one embodiment, the insulatingmaterial 144 comprises a polymer based insulating material as describedbelow. Other insulating materials 144 apparent to those who have skillin the art may be used.

In one embodiment, the substrate has a thickness of approximately 22microns and the cathode material 130 is disposed as a layer that has athickness of approximately 62 microns. The electrolyte material 132 isdisposed as a layer that has a thickness of between approximately 16 andapproximately 20 microns. The anode layer 134 may be a piece of lithiumthat has a thickness of approximately 38 microns. The first portion 146and the second portion 148 of the insulating material 144 are eachdisposed as a layer that has a thickness of approximately 22 microns.The anode tab 108 has a thickness of approximately 22 microns.

Various techniques may be used to dispose one or more of materials thatcomprise the battery 100 described above including coating, lithographicprinting, gravure printing, inkjet printing, pulsed laser deposition,magnetron sputtering, chemical vapor deposition, sol-gel processing, orthe like. It should be apparent to those who have skill in the art thatdifferent printing or other techniques may be used to dispose differentmaterials.

Although a rectangular battery 100 is described above, it should beapparent that other shapes of batteries 100 may be constructed in asubstantially identical manner. Referring to FIG. 7, a semicircularbattery 100 may be formed by applying the components of the battery 100described above onto a circular substrate 102, and then folding thecircular substrate 102 along the line 138.

Multi-cell batteries may also be manufactured by coupling batteries 100in parallel or serially. Referring to FIG. 8, a multi-cell battery 320having greater capacity than an individual battery 100 may beconstructed by forming batteries 100 onto a web 202 so that the cathodetabs 106 of the batteries 100 are conductively coupled to one another.Referring to FIG. 9, a multi-cell battery 322 having greater voltagethan an individual battery 100 may be constructed by forming batteries100 onto a web 202 so that the cathode tab 106 of each battery 100 ofthe multi-cell battery 322 is conductively coupled to the anode tab 108of another battery 100 of the multi-cell battery 322.

Instead of disposing materials onto a substrate 102 and folding thesubstrate 102 to form the battery 100, materials may be disposed onseparate substrate portions that are thereafter laminated together toform the battery 100. Referring to FIGS. 10 and 11, a battery comprisesa first conductive substrate portion 402 and a second conductivesubstrate portion 404. In the illustrated embodiment, the first andsecond conductive substrate portions 402, 404, respectively, arediscrete elements. This is in contrast to the construction of thebattery 100 wherein upper and lower portions 454 and 458, respectively,(FIG. 1) of the conductive substrate 102 are integral with one another.disposed on the substrate portion 402 are materials 406 that include,for example, a layer of cathode material 130, a layer of electrolytematerial 132, insulating material 144, and adhesive material 128.disposed on the substrate portion 404 are materials 408 that include,for example, a layer of cathode material 130, a layer of electrolytematerial 132, insulating material 144, adhesive material 128, an anodetab 108, and a layer of anode material 134. The two substrate portions402 and 404 are brought together so that adhesive material 128comprising the materials 406 contacts materials 408, and the adhesivematerial 128 comprising the materials 408 contacts materials 406. Theadhesive materials 128 disposed on the substrate portions 402 and 404are activated to form the battery 400.

Referring to FIG. 12, a web 420 comprising the substrate portion 402 maybe passed through a plurality of material applicators 422 that disposethe materials 406 on a side 424 of the web 420.

Similarly, a web 426 comprising the substrate portion 404 may be passedthrough a plurality of material applicators 428 that dispose thematerials 408 on a side 430 of the web 426. A turn unit 432 may be usedto turn the web 426 so that the side 430 of the web 426 faces the side424 of the web 420. A laminating unit 434 aligns the web 420 and the web426 so that the materials 406 and 408 disposed thereon, respectively,are in register, and laminates at least portions of the web 420 and 426to form unfinished batteries 436. The unfinished batteries 436 may beprocessed further to form finished batteries 400 as described above withrespect to the manufacture of batteries 100.

FIGS. 13A and 13B illustrate an embodiment wherein the anode tab 108 isdisposed on an exposed ledge or shoulder 410 of the battery 100 or 400.Specifically, the substrate portion 404 and elements 128, 130, and 144extend outwardly (i.e., to the right as seen in FIG. 13B) relative tothe substrate portion 402 and the elements 144 and 128 in the upperportion of FIG. 13B to define the ledge or shoulder of the battery 100or 400. In the illustrated embodiment, the adhesive material 128 may bedisposed between the insulating material 144 and the anode tab 108. Ifdesired, the insulating material 144 may be omitted, provided theadhesive material 128 is electrically insulating. As seen in FIG. 13A,the insulating material 144 may extend front-to-back by a distancegreater than or equal to the extent of the anode tab 108. The battery100 or 400 having the shoulder 410 may be otherwise identical to thebattery of FIGS. 1, 4, and 11. As shown at least in FIG. 13A, at least aportion of the anode tab 108 is exposed outside the battery 100 or 400so that an electrical load may be coupled thereto.

In some embodiments, the anode tab 108 and/or the insulating material144 may be applied using any application method as noted above includinglithography, gravure, inkjet, vapor deposition, and the like. It shouldbe apparent to one of skill in the art that the anode tab 108 and/or theinsulating material 144 may be applied selectively in order to customizethe battery 100 or 400. One or more portions of the substrate portions402 and 404 may be electrically coupled to one another, for example, bycrimping, an electrically conductive adhesive such as an epoxy, orotherwise.

The ledge or shoulder 410 may be formed in the battery 100 by foldingthe substrate about the fold section or portion 139 such that first andsecond edges 452 a and 452 b of the upper portion 454 (FIGS. 1 and 3A)align (i.e., are in register with) first and second edges 456 a and 456b of the lower portion 458 (the first edge 456 a is not visible in FIG.1). Third edges 452 c and 456 c are offset with respect to one another(the edges 452 c and 456 c, while shown in FIG. 1, are not illustratedas being offset in such FIG.). The ledge or shoulder 410 of the battery400 is formed similarly by aligning first through third edges 460 a-460c of the substrate portion 402 with first through third edges 462 a-462c, respectively, of the substrate portion 404 and offsetting fourthedges 460 d and 462 d of the substrate portions 402 and 404,respectively, by making the width of the substrate portion 402 shorterthan the width of the substrate portion 404. In some embodiments, onlythe first and second edges 460 a and 460 b of the substrate portion 402may be aligned with first and second edges 462 a and 462 b,respectively, of the substrate portion 404.

In some embodiments, the battery 100 or 400 described above may beencased in a suitable non-conductive material 463 such as, for example,a plastic or other a polymer, or other materials apparent to thoseskilled in the art (FIG. 2 shows a portion of the non-conductivematerial 463 encasing the battery 100). In such embodiments, the battery100 may be encased after the battery 100 has been folded into the foldedconfiguration, and/or laminated and sealed. The encasing material mayseal the entire battery 100 except for portions of the cathode tab 106and/or anode tab 108, which may be exposed outside of the encasingmaterial, either during the production process or thereafter. In thismanner, a load may be electrically coupled to the cathode tab 106 and/orthe anode tab 108, but the rest of the battery 100 may be encased toprotect such battery from the environment.

One or more techniques other than folding may be used in any of theembodiments disclosed herein to assemble/manufacture battery components.Such techniques include depositing, laying, fusing, adhering,laminating, or otherwise applying materials such as films, coatings,and/or planar, substantially planar, and/or non-planar components atopand/or beside one another either on or without an associated one or moresubstrates.

Adhesive Material

In one embodiment, the adhesive material 128 of the present applicationincludes a vinyl polymer and a solvent comprising toluene and xylene.Ink jet printing technology may be utilized to apply the adhesivematerial 128 to a substrate during the manufacture of a battery.

The adhesive material 128 may provide protection of the batterycomponents within the interior region 126 from water and othercontaminants in the final battery package. The adhesive material 128should have sufficient cohesion to resist tearing and delaminating afterthe battery is laminated. Degradation of the adhesive material 128 couldinterfere with the electronic and ionic transport and expose the lithiumor other anode material to the ambient environment, which could lead tobattery failure.

The adhesive material 128 may have flow characteristics to allow for inkjettability. Such flow characteristics may be defined by viscosity,surface tension, or fluid solids content. The viscosity may range fromabout 1.0 to 20.0 cP, preferably from about 1.0 cP to about 8.8 cP. Thesurface tension may range from about 25 mN/m to about 45 mN/m,preferably from about 27 mN/m to about 33 mN/m. The fluid solids content(NV) may range from about 0.1% to about 50%, preferably from about 1.5%to about 8.0%. In some embodiments, the adhesive material 128 is jettedfrom the print head at room temperature. In other embodiments, the printhead may be heated up to 65° F. to reduce viscosity. In furtherembodiments, the adhesive material 128 may be heated prior to deliveryto the print head.

In one embodiment, the adhesive material 128 may include from about 1.0%to about 8.0%, preferably from about 2.0% to about 7.0%, and mostpreferably from about 4.0% to about 5.0%, by weight of the vinylpolymer, and from about 1.0% to about 100.0%, preferably from about60.0% to about 100.0%, and most preferably from about 85.0% to about95.0%, by weight of the solvent. Once the adhesive material 128 isapplied to the substrate, a majority of the solvent is vaporized suchthat primarily the vinyl polymer remains. Vaporization includes anymaterial changes to the gaseous state by active means such as heat orother similar processes as well as by passive means such as evaporationor other similar processes. The substrate onto which the adhesivematerial 128 is jetted may be maintained at an elevated temperatureranging from about 23° C. to about 176° C., preferably about 280° F.(about 138° C.), to promote vaporization of the solvent. The componentsof the adhesive material 128 are preferably resistant and inert relativeto the battery components disposed on the substrate subsequent to thejetting of the adhesive material 128. In particular, the adhesivematerial 128 may be exposed to n-methyl-2-pyrrolidone (NMP) and gammabutyrolactone (GBL), or similar solvents, and may be relatively inertand unaffected by these solvents such that no degradation, such assoftening, discoloration, or dissolution, of the insulator materialoccurs.

The polymer should have adhesive qualities and be jettable. In oneembodiment, a polymer with an average number molecular weight in therange of about 30,000 to about 40,000 g/mol has these properties. Onepolymer suitable for use may be a terpolymer of ethylene, vinyl acetate,and maleic anhydride, such as Orevac 9305 by Arkema Chemical (King ofPrussia, Pa.). Other suitable polymers include polyethylene, ethylenecopolymers, copolymers of maleic anhydride, vinyl copolymers, copolymersof ethyl acrylate, ethylene acrylic acid, copolymers of ethylene acrylicacid, ethylene vinyl acetate, thermoplastic urethanes, polyvinylidenefluoride, ethylene acrylate, butyl acrylate, methyl acrylate,polyisobutene, polyolefins, styrene butadiene, copoly rosin,polyterpenes, poly styrenated terpenes, terpene phenolics, to name afew. Monomers that may be suitable for use with other polymers includemaleic anhydride, vinyl acetate, and ethyl acrylate, among others.

The solvent may include toluene and/or xylene. In one embodiment, thesolvent includes from about 1.0% to about 99.8%, preferably from about30% to about 70%, and most preferably from about 45% to about 55%, byweight of toluene, and from about 1.0% to about 100.0%, preferably fromabout 30% to about 70%, and most preferably from about 40% to about 45%,by weight of xylene. Under some circumstances, the ratio of toluene toxylene should range from 1.125:1 to 1.222:1 to improve the vaporizationof the solvent.

Other suitable solvents include p-cymene (4-isopropyl toluene) andanisole. In other embodiments, (methoxy benzene), dimethy formamide,cyclohexanone, anisole, n-methyl pyrrolidone, vinyl-pyrrolidone,mestylene (1,3,5-triethylbenzene), methyl ethyl ketone, propylenecarbonate, ethylene carbonate, propylene glycol pheny ether, propyleneglycol monomethyl ether acetate, dibasic ester, 1-tetradecene,octadecene, limonene and alpha turpineol, or similar compounds may beused.

If the polymer is subjected to a higher heat, for example, duringsubsequent lamination(s), a further polymer may be included to increaseheat resistance and prevent flow at higher temperatures and pressures.In some embodiments, the battery may undergo a lamination at 135° C. forseven minutes at 100 psig and/or a further lamination at 145° C. for sixminutes at 100 psig. In some embodiments, the polymer in the adhesivematerial 128 may have a melting point that is greater than thelamination temperature(s) while simultaneously having a sufficiently lowviscosity to allow for jetting. One indicator of heat resistance is themelt index of a polymer, which relates the molecular weight to the flowrate at a particular temperature. An adhesive material 128 that issubjected to lamination may have a combination of polymers havingcontrasting melt indices. For example, a polymer that has adhesivequalities and is jettable may have a high melt index such asapproximately 200 and a melting point such as about 68° C. This polymermay be mixed with a further polymer having a relatively lower melt indexsuch as approximately 7 and a melting point such as about 150° C. toobtain an adhesive material 128 that has adhesive properties, isjettable, and is sufficiently heat resistant.

One suitable heat-resistant polymer is a terpolymer of ethylene, ethylacrylate, and maleic anhydride such as Lotader 4700 by Arkema Chemical(Kind of Prussia, Pa.). In a sample embodiment, the adhesive material128 may include from about 0.1% to about 2.7%, preferably 0.5% to about1.6%, and most preferably from about 0.75% to about 0.9%, by weight ofthe further polymer. In this sample embodiment, the ratio of the polymerto the further polymer should range from 5.333:1 to 5.556:1 to maintaina good balance of viscosity and heat resistance. Other suitable polymersinclude those listed above. In other embodiments, a crosslinking agentsuch as peroxides may be included.

The adhesive material 128 may also include a surfactant to prevent theevaporation of solvents prior to jetting. The adhesive material 128 mayinclude an amount of up to about 10%, preferably between about 0.5% toabout 5%, or more preferably between about 0.3% and about 3%, by weightof a surfactant. Any type of surfactant may be useful to include in theadhesive material 128 to impart the desired properties includinganionic, nonionic, cationic, or other types of surfactants. One possiblesurfactant is an octylphenyl ethylene oxide condensate such as TritonX-45 by Dow Chemical (Midland, Mich.). Other suitable surfactantsinclude polyacrylates, fluorine modified acrylates, polysiloxanes,modified ethylene oxides, alkoxylated surfactants, sufosuccinates,acetylenic, alkyl polyglucosides, phosphate esters, and other highsurface tension solvents.

In other embodiments, the surface tension modifier is used to reducespreading. Preferably, dynamic surface tension ranges from about 25dynes/cm to about 45 dynes/cm. More preferably, a dynamic surfacetension ranges from about 29 dynes/cm to about 31 dynes/cm. Staticsurface tension ranges from about 25 dynes/cm to about 45 dynes/cm, andpreferably from about 27 dynes/cm to about 33 dynes/cm. The surfacetension modifier may include propylene glycol phenyl ether or dibasicester, among others.

Additional contemplated components in the adhesive material 128 includea surfactant, a polymer, a leveling agent, an inorganic compound, anorganic compound, dielectric particles, dielectric resins, or compoundsthat may incorporate electrically insulative properties, and/or anycombination thereof.

In some embodiments, the adhesive material 128 may be disposed in alayer having a thickness in the range from about 10 microns to about 12microns. This thickness may be obtained by making a number of passes ofthe printing unit over the substrate. In some embodiments, the thicknessmay be obtained by making up to about 50 passes, preferably up to about30 passes, and more preferably up to about 15 passes of the printingunit over the substrate, although the number of passes depends onvarious factors such as, for example, selection of the print head type,jetting performance, fluid solids content of the adhesive material 128,and mass flow rate.

The following example further illustrates the disclosure but, of course,should not be construed as in any way limiting its scope. An adhesivematerial 128 useful in the present disclosure was prepared as follows:

50.8 wt % Toluene

43.314 wt % Xylene

4.36 wt % Terpolymer of ethylene, vinyl acetate, and maleic anhydride(Orevac 9305)

0.84 wt % Terpolymer of ethylene, ethyl acrylate, and maleic anhydride(Lotader 4700)

0.69 wt % Octylphenyl ethylene oxide condensate (Triton X-45)

To prepare the adhesive material 128, the toluene and the xylene wereheated to approximately 90° on a hot plate fitted with a magneticstirrer. The polymer and the further polymer were sifted into the heatedsolvent in small increments with good agitation to prevent settling andgel encasement. Once the resins were in solution the ink was cooled toroom temperature and the surfactant was added. The ink was stirred foran additional 15 minutes. Prior to jetting, the adhesive material 128was filtered.

To evaluate performance, solvent testing, adhesion testing, and moisturetesting were conducted on the adhesive material 128. Solvent testing wasperformed by placing five drops of solvent on a dried film of theadhesive material 128. A watch glass was placed on top of the drops toprevent evaporation. The drops were evaluated at 2 hours and 24 hoursfor degradation of the adhesive film. Degradation had occurred if theadhesive softened, discolored, or dissolved. During the manufacture ofbattery packages, the adhesive material 128 was exposed to othersolvents at elevated temperatures. No degradation occurred.

Adhesion of the adhesive material 128 to the substrate was determined bytape tests, t-bends, and peel strength testing. The tape test tests theadhesion of the dried ink to the substrate. The adhesive material 128was coated onto a nickel-coated copper substrate and dried at 100° C.for 15 minutes. A piece of adhesive tape was adhered partially coveringthe adhesive and partially covering the uncoated nickel-coated coppersubstrate. The tape was removed quickly at a 150 degree angle. This testwas performed on hand draw downs using a Meyer rod to coat the adhesiveonto the substrate. The adhesive exhibited excellent adhesion.

T-bends were determined by folding the adhesive coated substratefoil-to-foil and creasing the edge. The crease was then examined using aloupe to determine if any of the adhesive was delaminated.

Peel strength adhesion was then tested using a Tag and LabelManufacturer's Institute (Amityville, Me.), Release and Adhesion testerfitted with grips to hold the battery substrate. A force gage fromMark-10 (Copiague, N.Y.), the M5-10 model, was attached to one of thegrips on the adhesion tester to measure peel strength. The battery wasattached by placing uncoated ends of the substrate into the grips. Thepeel tester was set at 12 inches/min. Data was collected using theMesur-Lite software (Copiague, N.Y.). Acceptable peel strengths werefound to be in the 2 lbs force range.

Moisture testing was determined using a spot test. Five drops of solventwere placed on a dried film of the adhesive material 128. A watch glasswas placed on top of the drops to prevent evaporation. The drops wereevaluated at 2 hours and 24 hours for degradation of the adhesive film.Degradation had occurred if the adhesive softened, discolored, ordissolved. During the manufacture of battery packages, the adhesivematerial 128 was exposed to other solvents at elevated temperatures. Nodegradation was detected.

Jetting capability was determined by balancing various solventcombinations for the ability to solubilize the polymer and producesurface tensions, evaporation rates, and viscosities that would becompatible with the Dimatix printhead by Fuji. The boiling points andevaporation rates of the selected solvent combination of xylene andtoluene provide a quick drying ink which does not require an additionaldrying step. The adhesive material 128 is capable of creating avoid-free continuous film with good edge definition.

Insulator Material

An insulator material 144 of the present application includes a polymerand a solvent. Ink jet printing technology may be utilized to apply theinsulator material 144 to a substrate during the manufacture of abattery.

The insulator material 144 should have sufficient cohesion to resisttearing and delaminating after the battery 100 is laminated. Degradationof the insulator material 144 could interfere with the electronic andionic transport and expose the lithium or other anode material to theambient environment, which could lead to battery failure.

The insulator material 144 may have flow characteristics to allow forthe insulator material 144 to be properly jetted from the print heads.Such flow characteristics may be defined by viscosity, surface tension,or fluid solids content (NV). The viscosity may range from about 1.0 to20.0 cP, preferably from about 3.4 cP to about 5.5 cP. The surfacetension may range from about 28 to about 45 mN/m. The fluid solidscontent may range from about 1.0% to about 40.0%, preferably from about5.0% to about 25.0%, and most preferably from about 15.0% to about19.0%. In some embodiments, the insulator material 144 is jetted fromthe print head at room temperature.

In one embodiment, the insulator material 144 may include from about0.25% to about 20.0%, preferably from about 0.5% to about 6.0%, and mostpreferably from about 0.75% to about 5.0%, by weight of the polymer, andfrom about 1.0% to about 99.75%, preferably from about 30.0% to about99.5%, and most preferably from about 57.0% to about 99.25%, by weightof the solvent. In another embodiment, the insulator material 144further comprises from about 10.0% to about 70%, preferably from about20.0% to about 50.0%, and most preferably from about 36.0% to about40.0%, by weight of a crosslinking agent.

Once the insulator material 144 is applied to the substrate, a majorityof the solvent is vaporized such that primarily the polymer remains.Vaporization includes any material changes to the gaseous state byactive means such as heat or other similar processes as well as bypassive means such as evaporation or other similar processes. Thesubstrate onto which the insulator material 144 is jetted may bemaintained at an elevated temperature ranging from about 80° C. to about300° C. for a duration of about 5 seconds to about 40 minutes,preferably from about 90° C. to about 115° C. for a duration of about 6minutes to about 8 minutes, to promote vaporization of the solvent. Insome embodiments, the substrate may be heated to about 180° F. (about82° C.) during application of the insulator material 144, and thenraised to about 210° F. (about 99° C.) to complete the drying process.The substrate and insulator material 144 may be further heated topromote cross-linking, if applicable. In this case, the substrate andinsulator material 144 may be heated at a temperature of from about 80°C. to about 300° C. for a duration of about 2 minutes to about 120minutes, preferably at a temperature of about 95° C. to about 115° C.for a duration of about 5 minutes to about 10 minutes, and mostpreferably at a temperature of about 110° C. for a duration of about 6minutes to about 8 minutes.

In one embodiment, the components of the insulator material 144 may beresistant and inert relative to the battery components disposed on thesubstrate subsequent to the jetting of the insulator material 144. Inparticular, the insulator material 144 may be exposed ton-methyl-2-pyrrolidone (NMP) and gamma butyrolactone (GBL), or similarsolvents, and may be relatively inert and unaffected by these solventssuch that no degradation, such as softening, discoloration, ordissolution, of the insulator material 144 occurs.

The polymer suitable for use may be a linear copolyester, such asDynapol 912 by Evonik Corp. (Parsippany, N.J.) or a poly(amide imide),such as Torlon 4000T-HV and/or Torlon 4000T-LV by Solvay (Houston,Tex.). Other suitable polymers include polyesters, polyethylene,polycarbonate, polyester-polycarbonate copolymers, epoxies, silicones,polyurethanes, polysilfides, cyanoacrylates, ethylene-propylene dienemonomers (EPDM), CE cycloaliphatic epoxy, andparylene(poly(p-xylene)polymers, to name a few. In one embodiment, theinsulator material 144 includes from about 1% to about 20%, preferablyabout 3% to about 5%, and more preferably from about 3.5% to about 4%,by weight of a linear copolyester. In another embodiment, the insulatormaterial 144 includes from about 0.5% to about 10.0%, preferably fromabout 0.75% to about 5%, and more preferably from about 1% to about 4%,by weight of a poly(amide imide).

The solvent may include NMP, toluene, and/or xylene. In one embodiment,the insulator material 144 includes from about 1.0% to about 99.0%,preferably from about 10.0% to about 50.0%, and most preferably fromabout 19.0% to about 20.0%, by weight of toluene, and from about 1.0% toabout 99.0%, preferably from about 10.0% to about 50.0%, and mostpreferably from about 19.0% to about 20.0%, by weight of xylene. Undersome circumstances, the ratio of toluene to xylene should beapproximately 1:1 to improve the vaporization of the solvent. In anotherembodiment, the insulator material 144 includes from about 1.0% to about99.75%, preferably from about 30.0% to about 99.5%, and most preferablyfrom about 57.0% to about 99.25%, by weight of NMP.

Other suitable solvents include p-cymene (4-isopropyl toluene),mestylene (1,3,5-triethylbenzene), and anisole(methoxy benzene). Inaddition, further alternative solvents include dimethy formamide,cyclohexanone, anisole, n-methyl pyrrolidone, vinyl-pyrrolidone, methylethyl ketone, propylene carbonate, ethylene carbonate, propylene glycolpheny ether, propylene glycol monomethyl ether acetate, dibasic ester,tetradecene, octadecene, limonene and alpha turpineol, or similarcompounds.

In some circumstances, the insulator material 144 may include one ormore crosslinking agent(s) to increase heat resistance. In someembodiments, the battery is laminated at 135° F. for seven minutes at100 psig. In other embodiments, the battery may undergo a secondlamination. One suitable crosslinking agent is an isophoronediisocyanate 3,5-dimethylpyrazole such as Trixene BL7960 (Schaumburg,Ill.). Another suitable crosslinking agent is isophorone diisocyanatedi-ethyl malonate such as Trixene BL7963 (Schaumburg, Ill.). In a sampleembodiment including isophorone diisocyanate 3,5-dimethylpyrazole andisophorone diisocyanate di-ethyl malonate, the ratio of the isophoroisophorone diisocyanate 3,5-dimethylpyrazole to the isophoronediisocyanate di-ethyl malonate should be 1:1 to maintain a good balanceof viscosity and heat resistance. Alternative crosslinking agentsinclude polyester polyols, triglycidal isocyanates, melamines,benzoguanamine, n-butylated urea, caprolactam, methyl ethyl ketoxime,di-ethyl malonate, 3,5-dimethylpyrazole, uretidione, isopohoronediisocyanate, 1,6-hexamethylene diisocyanate, and other similarcompounds.

The insulator material 144 may include an additional solvent tosolubilize the one or more crosslinking agent. One possible solvent iscyclohexanone, although alternatives include toluene, xylene, and theother solvents listed above. Further, a catalyst may be included in theinsulator material 144 to initiate cross-linking. One suitable catalystis the Borchi Kat 315, bismuth neodecanoate by OMG Borchers (Westlake,Ohio). Other possible catalysts include organo zinc complexes, bismuthneodecanaote, organo zinc complexes, potassium acetate, potassiumoctoate, bismuth carboxylate, dibutyl tin oxide, aluminum chelates,zirconium chelates, stannous octoate, and dibutyltin dilaurate, amongothers.

Preferably, dynamic surface tension ranges from about 25 dynes/cm toabout 45 dynes/cm. More preferably, a dynamic surface tension rangesfrom about 29 dynes/cm to about 31 dynes/cm. Static surface tensionranges from about 25 dynes/cm to about 45 dynes/cm, and preferably fromabout 27.5 dynes/cm to about 29 dynes/cm. The surfactant is anoctylphenyl ethylene oxide condensate such as Triton X-45 by DowChemical (Midland, Mich.).

Additional contemplated components in the insulator material 144 includea surfactant, a polymer, a leveling agent, an inorganic compound, anorganic compound, and/or any combination thereof.

The layer of insulator material 144 may be formed by multiple passes ofa print head in order to obtain the desired thickness having sufficientresistance. In some embodiments, the thickness may range from about 20microns to about 100 microns, preferably about 35 microns to about 45microns in some embodiments. The electrical resistance should be greaterthan about 125 megaohms, preferably greater than about 550 megaohms.

The following examples further illustrate the disclosure but, of course,should not be construed as in any way limiting its scope. Insulatormaterials 144 useful in the present disclosure were prepared as follows:

Example 1

3.85 wt % Linear copolyester

19.11 wt % Toluene

19.11 wt % Xylene

19.89 wt % Cyclohexanone

19.02 wt % Isophorone diisocyanate 3,5-dimethylpyrazole

19.02 wt % Isophorone diisocyanate di-ethyl malonate

Example 2

2-4 wt % Linear poly(amide imide) (Torlon 4000T-LV)

96-98 wt % Solvent (NMP)

Example 3

1-3 wt % Linear poly(amide imide) (Torlon 4000T-H)

97-99 wt % Solvent (NMP)

To prepare the insulator material 144, the solvent(s) was heated toapproximately 90° on a hot plate fitted with a magnetic stirrer. Thepolymer was sifted into the heated solvent in small increments with goodagitation to prevent settling and gel encasement. Once the resins werein solution the ink was cooled to room temperature and the crosslinkingagents were added. The ink was stirred for an additional 15 minutes.Prior to jetting, the insulator material 144 was filtered.

To evaluate performance, solvent testing, adhesion testing, moisturetesting, and testing of the electrical insulative properties wereconducted on the insulator material 144. Solvent testing was performedby placing five drops of solvent on a dried film of the insulatormaterial 144. A watch glass was placed on top of the drops to preventevaporation. The drops were evaluated at 2 hours and 24 hours fordegradation of the insulator film. Degradation had occurred if theinsulator softened, discolored, or dissolved. During the manufacture ofbattery packages, the insulator material 144 was exposed to othersolvents at elevated temperatures. No degradation occurred.

Adhesion of the insulator material 144 to the substrate was determinedby tape tests and t-bends. For the tape tests, the insulator material144 was coated onto a nickel-coated copper substrate and dried at 100°C. for 15 minutes. A piece of adhesive tape was adhered partiallycovering the insulator and partially covering the uncoated nickel-coatedcopper substrate. The tape was removed quickly at a 150 degree angle.The insulator exhibited excellent adhesion.

T-bends were determined by folding the insulator coated substratefoil-to-foil and creasing the edge. The crease was then examined using aloupe to determine if any of the insulator was delaminated. Theinsulator appeared continuous and well adhered to the nickel-coatedcopper substrate

Moisture testing was determined using a spot test. Five drops of solventwere placed on a dried film of the insulator material 144. A watch glasswas placed on top of the drops to prevent evaporation. The drops wereevaluated at 2 hours and 24 hours for degradation of the insulator film.Degradation had occurred if the insulator softened, discolored, ordissolved. During the manufacture of battery packages, the insulatormaterial 144 was exposed to other solvents at elevated temperatures. Nodegradation was detected.

The electrical insulative properties were determined by coating andcuring the insulator on aluminum foil. The electrical resistance wasthen tested using three methods. The first method utilized the Flue 1507Insulation Tester. The negative probe was clamped onto the bare aluminumand the positive probe was touched to the coated insulator. Theinsulator had an electrical resistivity up to 550 megaohms at athickness of 2 to 3 microns. The second method used the Vitrek V61Tester. The negative probe was clamped onto the bare aluminum and thepositive probe was clamped onto the insulator. The sample was tested forfive seconds with a current of 3 mA and a voltage of 0.1 kV. Voltage wasthen raised to 0.5 kV, and the sample was retested. This test passed at465 megaohms 3. The third test is building a working battery. All thelayers of the battery were applied, and the battery was laminated at110° C. for 3 seconds at 50 PSI (laminator cylinder pressure). Thebattery was then tested for continuity and passed.

Jetting capability was determined by balancing various solventcombinations for the ability to solubilize the polymer and producesurface tensions, evaporation rates, and viscosities that would becompatible with the Dimatix printhead by Fuji. The boiling points andevaporation rates of the selected solvent combination of xylene andtoluene provide a quick drying ink which does not require an additionaldrying step. The insulator material 144 is capable of creating avoid-free continuous film with good edge definition.

Cathode Material

In another embodiment, the cathode material 130 may include an activematerial, a carbon material, a binder polymer, an ionic salt, adispersant, and a solvent. Ink jet printing technology may be utilizedto apply the cathode material 130 to a substrate during the manufactureof a battery.

The cathode material 130 may have flow characteristics to allow for thecathode material 130 to be properly jetted from the heads. Such flowcharacteristics may be defined by viscosity, surface tension, fluidsolids content (NV), and particle size distributions. The viscosity, inparticular at the time of application of the cathode material 130 ontothe substrate, may range from about 3.0 to 30.0 cP, preferably fromabout 3.0 cP to about 20.0 cP. The surface tension may range from about30 dynes/cm to about 50 dynes/cm. The fluid solids content (NV) mayrange from about 2.5% to about 25.0%, preferably from about 5.0% toabout 15.0%, and most preferably from about 7.5% to about 10.0%.Further, the cathode material 130 may be jetted from the print head atroom temperature in some embodiments. In other embodiments, the printhead may be heated to about 25° C. to about 55° C., preferably about 43°C.

In addition to the flow characteristics of the materials, the particlesize distribution of the dispersed components such as the activematerial and carbon material(s), may be important to the jettability ofthe cathode composition. The 95^(th) percentile of the particle sizedistribution of the materials ranging from about 0.300 microns to about3.000 microns may preclude the presence of large particles that couldclog the ink jet print heads. Additionally, the process formanufacturing the cathode material 130 can be modified to optimize theparticle size of the dispersed components. Modifications to the millingprocess are described in the examples below.

Further, other properties such as resistance and adhesion wereconsidered in evaluating the cathode material 130. The resistance perthickness of the material may be up to about 1.0 ohm/micron, preferablyup to about 0.5 ohm/micron. Adhesive failure refers to the separation ofthe cathode material 130 from the substrate. Cohesive failure refers tothe separation of the cathode material 130 from itself.

In one embodiment, the cathode material 130 may include from about 5.0%to about 20.0%, preferably from about 7.0% to about 15.0%, by weight ofan active material; from about 0.1% to about 5.0%, preferably from about0.25% to about 2.5%, by weight of a carbon material; from about 0.25% toabout 5.0%, preferably from about 0.5% to about 2.5%, by weight ofbinder polymer; from about 0.5% to about 5.0%, preferably from about1.0% to about 3.0%, by weight of an ionic salt; from about 50.0% toabout 94.05%, preferably from about 80.0% to about 90.0%, by weight of asolvent or solvent mixture, and from about 0.1% to about 6.0%,preferably from about 0.2% to about 4.0%, by weight of dispersant. Thecathode material 130 may also include up to about 6.0%, preferably fromabout 0.2% to about 4.0%, by weight of surfactant.

Once the cathode material 130 is applied to the substrate, a majority ofthe solvent may be vaporized. Vaporization includes material changes tothe gaseous state by active means such as heat or other similarprocesses as well as by passive means such as evaporation or othersimilar processes. The substrate onto which the cathode material 130 isjetted may be maintained at an elevated temperature from about 25° C. toabout 200° C., preferably at about 145° C., to promote vaporization ofthe solvent. The temperature of the print head and/or the substrate mayvary depending on the solvent.

The active material suitable for use may be an electrolytic manganesedioxide. Other possible active materials include iron sulfide, irondisulfide, copper iron sulfide, carbon monofluoride, silver chromate,silver oxide plus vanadium pentoxide, copper (III) oxide, coppersulfide, lead bismuthate, bismuth trioxide, vanadium pentoxide, andcobalt oxide, and other similar materials. The particle sizedistribution is measured using a dynamic laser light scatteringapparatus such as a Nanotrac model 252 (Microtrac Corporation,Montgomeryville, Pa.). MV is the mean volume distribution particle size,D50 is the 50^(th) percentile volume distribution particle size, and D95is the 95^(th) percentile volume distribution particle size. Exampleparticle size distribution results of the active material are shown inTables 1, 3, and 4. In a sample embodiment, the active material has anaverage particle size of less than about 0.5 microns and is free ofparticles greater than 3.0 microns.

TABLE 1 active material wt. % dispersant (s) wt % solvent wt. % MV D50D95 electrolytic MnO₂ 25.0 BYKJET-9133 2.0 N-methyl-2- 73.0 0.259 0.2410.458 pyrrolidinone (NMP) electrolytic MnO₂ 25.0 BYKJET-9133 2.0 gamma73.0 0.203 0.199 0.310 butyrolactone (GBL)

Carbon material may be added to the cathode material 130 to improveelectrical conductivity and ion mobility. Carbon materials are definedas carbon blacks, acetylene blacks, graphites, graphenes, carbonnanotubes, all other structural variation of carbon, and mixturesthereof. In one embodiment, the cathode material 130 includes one ormore of the following carbon blacks: Timcal Ensaco 350G, Akzo NobelKetjenblack EC-300J, Timcal C-Nergy Super C65, and Evonik Arosperse 7.Other suitable carbon blacks include Timcal C-Nergy Super C45, TimcalSuper P-Li, and Denka Japan Denka Black Acetylene black. In someembodiments, the cathode material 130 may include up to about 5.0%,preferably up to about 2.5%, by weight of a graphite. Example particlesize distribution results of the carbon materials are shown in Tables2-4. In a sample embodiment, the carbon material has an average particlesize of less than about 0.5 microns and is free of particles greaterthan 3.0 microns. In some embodiments, it may be desired to maintain aratio of carbon material to active material between about 1 to 4 andabout 1 to 25, preferably between about 1 to 10 and about 1 to 20, morepreferably between about 1 to 13 and about 1 to 15.

TABLE 2 Carbon Material wt. % Dispersant (s) wt % Solvent wt. % MV D50D95 Timcal C-Nergy 6.0 Solsperse 76400 1.8 NMP 91.3 0.318 0.232 0.846Super C65 carbon Solsperse 12000 0.9 black Timcal Ensaco 350G 3.0polyvinyl 1.5 NMP 95.5 0.350 0.277 0.659 carbon black pyrrolidinone 15kMW Akzo Nobel 3.0 polyvinyl 1.5 NMP 95.5 0.315 0.251 0.876 KetjenblackEC-300J pyrrolidinone 15 kMW Asbury grade 4827 3.0 Solsperse 76400 1.5NMP 94.75 0.481 0.267 2.569 graphite Solsperse 5000 0.75 EvonikArosperse 7 3.0 Makon 10 1.5 NMP 95.5 0.235 0.225 0.359 carbon blackTimcal Ensaco 350G 3.0 Disperbyk-2155 2.25 NMP 94.75 0.297 0.270 0.540carbon black Akzo Nobel 3.0 Disperbyk-2155 4.5 NMP 92.5 0.377 0.2970.776 Ketjenblack EC-300J Timcal C-Nergy 6.0 Solsperse 76400 1.8 GBL91.3 0.309 0.284 0.590 Super C65 carbon Solsperse 12000 0.9 black EvonikArosperse 7 3.0 Solsperse 76400 0.30 GBL 96.55 0.302 0.301 0.492 carbonblack Solsperse 12000 0.15

The binder polymer may provide cohesion and adhesion of the cathode tothe conductive substrates. The polymer suitable for use may be apolyimide, such as a terpolymer poly(1,2,4,5-Benzetetracarboxylicdianhydride-co-4,4′-methylenebis(2,6-dimethylaniline)-co-2,4-diaminomesitylene)imide(poly(PDMA+TMMDA/DAMs)imide) by Solicore, Inc. (Lakeland, Fla.), andformed by reacting PMDA, 33.3 mole % DAMs and 66.7 mole % TMMDA. Anothersuitable polymer is a polyimide such as Matrimid 5218 by Huntsman (SaltLake City, Utah). Other suitable polymers include a functionalizedpolyvinylidene fluoride homopolymer such as Kynar ADX by Arkema Chemical(King of Prussia, Pa.), a polyvinylidene fluoride homopolymer such asKynar HSV 900 by Arkema Chemical (King of Prussia, Pa.), apolyvinylidene fluoride homopolymer such as Kynar 761 by Arkema Chemical(King of Prussia, Pa.), a polyvinylidene fluoride copolymer such asKynar 2751 by Arkema Chemical (King of Prussia, Pa.), a polyvinylidenefluoride homopolymer such as Fluor Solef 5130 by Solvay (Houston, Tex.),a polyvinylidene fluoride homopolymer such as KF by Kureha (New YorkCity, N.Y.), a VDF/TFE copolymer such as VT-475 by Daikin (Decatur,Ala.), a poly(vinylidene fluoride-tetrafluoroethylene-propylene) such asDyneon BRE-7131X by 3M (St. Paul, Minn.), a poly(vinylidene fluoride)such as D-1 by Targray (Montreal, Canada), polyamide-imides, such assuch as Torlon 4000T by Solvay (Houston, Tex.), to name a few. Mixturesof polymers may also be employed.

The ionic salt enables ion diffusion to and reaction with the activematerial. In some circumstances, the ionic salt may be a lithium salt ora lithium salt mixture. In one embodiment, the ionic salt may be lithiumbis trifluoromethanesulfonimide (LiTFSI) such as HQ-115 by 3M (St. Paul,Minn.). Other suitable salts such as LiCl, LiBr, LiI, LiPF₆, LiClO₄,LiB(C₂O₄)₂, LiAsF₆, LiBF₄, LiN(SO₂CF₂CF₃)₂, or LiCF₃SO₃, may be used. Inother embodiments, a lithium salt having a lower metal substratecorrosivity may be used.

The solvent may be N-methyl-pyrrolidone (NMP). Other suitable solventsinclude gamma butyrolactone, n-gamma valerolactone,N-methyl-2-pyrrolidinone, 3-methyl-oxazolidinone, tetramethylurea,dimethylsulfoxide, dimethylformamide, dimethylacetamide,methylethylketone, methyl isobutyl ketone, ethylene carbonate, propylenecarbonate, dimethylcarbonate, ethylmethylcarbonate, diethylcarbonate,dimethoxyethane, dimethoxymethane, diethoxyethane, tetrahydrofuran,2-methyl-tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane,2-methyl-1,3-dioxolane, acetonitrile, methylacetate, ethylacetate,methyl butyrate, ethyl butyrate, or any anhydrous, polar aprotic solventand mixtures thereof. The evaporation rate of the solvent may range fromabout 0.01 to about 1.0, preferably from about 0.02 to about 0.1 at 25°C. based on the evaporation rate scale where n-butyl acetate=1.0 at 25°C.

The cathode material 130 may include a dispersant to aid in thereduction of particle size and stabilize the particle size distribution.It may be desirable for the carbon material to have a high surface area,which corresponds to a small particle size, in order to promoteelectronic conduction. The increased surface area of the active materialis desired in some circumstances, as it increases the availability ofthe material to react with the ionic salt. The high surface area ofactive material and carbon materials creates a dispersion problem inthat the tendency of the particles to recombine, agglomerate, andflocculate is increased with increasing surface area. This can lead topoor jetting performance in and cause settling of the cathodecomposition prior to jetting. Therefore, in some embodiments, carefulselection of the amount and quantity of dispersant to effectivelystabilize the dispersed particles in the solvent is undertaken. In oneembodiment, the dispersant may be a polyethylene oxide adduct of octylphenol such as Stepan Makon 10 from Stepan Company or Triton X 100 fromSigma-Aldrich. Another suitable dispersant is a polyvinyl pyrrolidinonehaving a molecular weight between 5,000 and 20,000 g/mol such as PVP 15Kfrom International Specialty Polymers. Other suitable dispersants arehyperdispersants such as Lubrizol Solsperse 5000, 12000, 41000 or 76400from Lubrizol Advanced Materials Inc. Other suitable dispersants includepolymeric dispersants with pigment affinic groups such as BYKJET-9133,BYKJET-9151, Disperbyk-130, Disperbyk-2050, Disperbyk-2117,Disperbyk-2150, Disperbyk-2155, and Disperbyk-2164 from BYK Chemie, orany nonionic, anionic, cationic, amphoteric dispersant and mixturesthereof suitable for dispersing carbon blacks, graphite, graphene,carbon nanotubes, and inorganic compounds. In one embodiment, the activematerial may be milled in a dispersion including a dispersant such asBYKJET-9133 or Disperbyk-130. In another embodiment, one or more of thecarbon materials may be milled in a dispersion including a dispersantsuch as Makon 10 by Stepan, Solsperse 5000, 12000, and/or 76400 byLubrizol, or 15 kMW polyvinyl pyrrolidinone. In some embodiments, thedispersants preferably may not adversely affect adhesion of the cathodelayer to the substrate, cohesion of the substrate layer, electricalconductivity and ionic mobility.

The cathode material 130 may include one or more surfactants to improvewetting of the cathode when jetted onto the substrate. Preferably,dynamic surface tension ranges from about 30 dynes/cm to about 50dynes/cm. Static surface tension ranges from about 30 dynes/cm to about50 dynes/cm. One suitable surfactant is Surfynol 61 by Air Products.Other potential surfactants include any nonionic, anionic, cationic,amphoteric surfactants and mixtures thereof suitable for controllingliquid surface tension and/or providing for improved wetting of metalsubstrate surfaces by the cathode composition.

In some embodiments, an adhesion promoting agent may be included toenhance bonding to unprimed metal surfaces.

The layers of the cathode material 130 may be formed by multiple passesof the print head(s) in order to obtain the desired thickness. In someembodiments, the thickness may range from about 40 to about 80 microns,preferably from about 60 microns to about 65 microns. This thickness maybe obtained by making up to 120 passes, preferably up to about 100passes, and more preferably between about 50 passes and 90 passes, ofthe printing unit over the substrate, although the number of passes isdependent on various factors such as, for example, selection of theprint head type, jetting performance, fluid solids content of thecathode material 130, and mass flow rate.

The following examples further illustrate the disclosure but, of course,should not be construed as in any way limiting its scope. It should benoted that the method of preparing the cathode materials 130 may bemodified as necessary depending on the size of the batch.

One embodiment of the cathode material 130, Example 1, useful in thepresent disclosure was prepared in accordance a Process A as shown inFIG. 14.

To prepare the cathode material 130, a dispersion of 27% by weightSurfynol 61 was admixed with 73% by weight dry N-methyl-2-pyrrolidinone(NMP) to form a solution having a weight of 26.52 g. A 5% by weightdispersion of the binder polymer was slowly added to 95% by weight NMPdispersion with vigorous stifling for approximately 16 to 24 hours toassure complete dissolution, forming a solution having a weight of163.92 g. Next, the liquid ingredients were loaded into the cathodemillgrind premix. The dry components including 6.6 g of carbon black,3.3 g of graphite, and 138.06 g of dry beta form manganese dioxide and261.60 g of NMP were added to the premix with stirring.

The premix was then charged into a stirred media mill by EMI EngineeredMills Inc. loaded with 1 mm yttrium stabilized zirconium beads. Othersize beads may be used to optimize the particle size achieved. Atemperature control bath connected to the mill maintained thetemperature during milling between about 25° C. and about 35° C. Duringthe media milling, particle agglomerates were broken up and amicroscopically uniform composition was achieved. The premix wasrecirculated in the mill at 1000 to 1500 rpm for about 10 minutes todisplace air from the system. The cathode millgrind was processed forabout 75 minutes at 2700 to 2730 rpm with continuous recycling. As shownin FIG. 14, about 156.92 g of the millgrind was discharged. About 1.35 gof lithium salt, about 2.64 g of the dispersant BYK-9133, and about139.1 g of dry NMP were then admixed to complete assembly of the cathodecomponents.

Finally, the cathode composition was processed using a high shear rotaryhomogenizer such as an Omni Mixer or IKA Ultra Turrax for 20 minutes atabout 8000 rpm. The cathode material 130 was filtered through a solventresistant 10 micron nominal membrane filter such as apolypropylene/polyethylene filter by Pall Corp.

The shelf life of the material of Example 1 is approximately 24 hours.

A further embodiment of the cathode material 130, Example 2, useful inthe present disclosure was prepared in accordance a Process B as shownin FIG. 15.

The final composition of Example 2 is the same as the final compositionof Example 1. The process of manufacturing differs in that the millingprocesses for each dispersed component including the carbon blacks,graphite, and manganese dioxide, were separated. This separation allowedfor selection of an optimum milling aid or dispersant specific for eachcomponent, and likewise optimization of the milling process as well asoptimization of the final formulation. The average particle sizes areprovided in Table 3 below.

TABLE 3 Component Average particle size Active material About 0.100microns to about 0.500 microns Carbon black About 0.100 microns to about0.500 microns Graphite About 0.200 microns to about 3.000 microns

In another embodiment, the binder polymer and solvent may be addedsubsequently to a mixture of the active material, carbon material, andlithium salt components. The active material may have an averageparticle size in the range from about 0.100 microns to about 0.500microns, and the carbon black may have an average particle size in therange from about 0.100 microns to about 0.500 microns. In a stillfurther embodiment, the polymer, or a mixture of the polymer and asolvent, may be provided with the mixture of the active material, carbonmaterial, and lithium salt components prior to the addition of thesolvent.

Examples 1-7 and Comparative Examples 1 and 2

Details of Examples 1 and 2 described above are provided in Table 4below. Additionally, Examples 3-7 and Comparative Examples 1 and 4 wereprepared in accordance with either process A or process B of FIGS. 14and 15, respectively, as identified in Table 4 below. While each ofExamples 1-7 include the general components of carbon black, an activematerial, a binder polymer, and a solvent, the specific components suchas different brands or product lines of each general component ofExamples 1-7 vary as shown in Table 4. The details of Examples 1-7 andComparative Examples 1 and 2 are provided in Table 4.

TABLE 4 millgrind(s) cathode ink process millgrind % > % > ink ID (A orB) component wt. % ID MV D50 D95 3 nm component wt. % MV D50 D95 3 nmExample 1 A Carbon black (Ensaco 350G) 0.55 KB01-78-stnd Carbon black(Ensaco 350G) 0.29 0.954 0.404 5.93 9.78 KB01-78-INK Carbon black(Ketjen) 0.55 Carbon black (Ketjen) 0.29 std. formula Graphite (TimrexKS4) 0.55 Graphite (Timrex KS4) 0.29 & process MnO₂ 23.01 MnO₂ 12.04poly(PDMA + TMMDA/DAMs)imide 1.37 poly(PDMA + TMMDA/DAMs)imide 0.72Surfynol 61 1.19 Surfynol 61 0.62 NMP 72.78 LiTFSI 0.45 BYK-9133 0.88NMP 84.43 Example 2 B Carbon black (Ensaco 350G) 3.00 KB01-75-Ensaco0.350 0.277 0.659 0.00 Carbon black (Ensaco 350G) 0.29 0.435 0.406 0.6790.00 KB01-79-INK polyvinylpyrrolidone 15K MW 1.50 KB01-75-Ketjen 0.3150.251 0.876 0.00 Carbon black (Ketjenblack) 0.29 NMP 95.50KB01-77-Timrex 3.21 3.63 6.33 48.55 Graphite (Timrex KS4) 0.29 Carbonblack (Ketjen) 3.00 KB01-78-MnO2 0.374 0.334 0.722 0.00 MnO₂ 12.04polyvinylpyrrolidone 15K MW 1.50 poly(PDMA + TMMDA/DAMs)imide 0.72 NMP95.50 polyvinylpyrrolidone 15K MW 1.32 Graphite (Timrex KS4) 15.00LiTFSI 0.45 polyvinylpyrrolidone 15K MW 7.50 BYK-9133 0.96 NMP 77.50 NMP83.64 MnO₂ 25.00 BYK-9133 2.00 NMP 73.00 Example 3 B Carbon black(Timcal Super C65) 6.00 KB01-58-C65-2 0.373 0.305 0.906 0.00 Carbonblack (Timcal Super C65) 0.88 0.448 0.368 0.713 0.00 KB01-81-INKSolsperse 76400 1.80 KB01-80-MnO2 0.327 0.305 0.551 0.00 Solsperse 764000.26 Solsperse 12000 0.90 Solsperse 12000 0.13 NMP 91.30 MnO₂ 12.04 MnO₂25.00 poly(PDMA + TMMDA/DAMs)imide 0.72 BYK-9133 2.00 LiTFSI 0.45 NMP73.00 BYK-9133 0.96 NMP 84.56 Example 4 B Carbon black (Ensaco 350G)3.00 KB01-75-Ensaco 0.350 0.277 0.659 0.00 Carbon black (Ensaco 350G)0.44 0.312 0.302 0.485 0.00 KB01-82-INK polyvinylpyrrolidone 15K MW 1.50KB01-75-Ketjen 0.315 0.251 0.876 0.00 Carbon black (Ketjenblack) 0.44NMP 95.50 KB01-80-MnO2 0.327 0.305 0.551 0.00 MnO₂ 12.04 Carbon black(Ketjen) 3.00 poly(PDMA + TMMDA/DAMs)imide 0.72 polyvinylpyrrolidone 15KMW 1.50 polyvinylpyrrolidone 15K MW 0.66 NMP 95.50 LiTFSI 0.45 MnO₂25.00 BYK-9133 0.96 BYK-9133 2.00 NMP 84.29 NMP 73.00 Example 5 B Carbonblack (Timcal Super C65) 6.00 KB01-58-C65-2 0.373 0.305 0.906 0.00Carbon black (Timcal Super C65) 0.44 0.470 0.321 1.222 0.50 KB01-83-INKSolsperse 76400 1.80 KB01-75-Ensaco 0.350 0.277 0.659 0.00 Carbon black(Ensaco 350G) 0.44 Solsperse 12000 0.90 KB01-80-MnO2 0.327 0.305 0.5510.00 MnO₂ 12.04 NMP 91.30 poly(PDMA + TMMDA/DAMs)imide 0.72 Carbon black(Ensaco 350G) 3.00 Solsperse 76400 0.13 polyvinylpyrrolidone 15K MW 1.50Solsperse 12000 0.07 NMP 95.50 polyvinylpyrrolidone 15K MW 0.22 MnO₂25.00 BYK-9133 0.96 BYK-9133 2.00 LiTFSI 0.45 NMP 73.00 NMP 84.53Example 6 B Carbon black (Timcal Super C65) 6.00 RG01-11 0.318 0.2320.846 0.00 Carbon black (Timcal Super C65) 0.88 0.479 0.392 1.125 0.00JB01-56-1 Solsperse 76400 1.80 RG01-09 0.194 0.179 0.374 0.00 Solsperse76400 0.26 repeat of KB01-81-INK Solsperse 12000 0.90 Solsperse 120000.13 NMP 91.30 MnO₂ 12.04 MnO₂ 25.00 poly(PDMA + TMMDA/DAMs)imide 0.72BYK-9133 2.00 LiTFSI 0.45 NMP 73.00 BYK-9133 0.96 NMP 84.56 Example 7 BCarbon black (Timcal Super C65) 6.00 RG01-11 0.318 0.232 0.846 0.00Carbon black (Timcal Super C65) 0.88 0.491 0.339 1.668 0.06 JB01-56-2Solsperse 76400 1.80 RG01-09 0.194 0.179 0.374 0.00 Solsperse 76400 0.26Solsperse 12000 0.90 Solsperse 12000 0.13 NMP 91.30 MnO₂ 12.04 MnO₂25.00 Kynar ADX-111 0.72 BYK-9133 2.00 LiTFSI 0.45 NMP 73.00 BYK-91330.96 NMP 84.56 Comparative B Carbon black (Arosperse 7) 3.00 RG01-160.235 0.225 0.359 0.00 Carbon black (Arosperse 7) 0.88 0.361 0.303 0.6600.00 Example 1 Makon 10 1.50 RG01-22 0.234 0.216 0.407 0.00 Makon 100.44 JB01-58-1 NMP 95.50 MnO₂ 12.00 MnO₂ 25.00 poly(PDMA +TMMDA/DAMs)imide 0.72 BYK-9133 2.00 LiTFSI 0.45 NMP 73.00 BYK-9133 0.96NMP 84.55 Comparative B Carbon black (Arosperse 7) 3.00 RG01-16 0.2350.225 0.359 0.00 Carbon black (Arosperse 7) 0.88 Example 2 Makon 10 1.50RG01-22 0.234 0.215 0.407 0.00 Makon 10 0.44 JB01-58-2 NMP 95.50 MnO₂12.00 MnO₂ 25.00 Kynar ADX-111 0.72 BYK-9133 2.00 LiTFSI 0.45 NMP 73.00BYK-9133 0.96 NMP 84.55

Examples 1-7 and Comparative Examples 1 and 2 were tested for viscosity,resistance, and adhesion. The results are provided in Table 5 below.

TABLE 5 Viscosity at 45° C., Resistance/Coating Adhesion/Cohesion 50 rpm(cP) Thickness (W/mm) Tape Test Example 1 11.6 0.120 significantcohesive failure Example 2 12.90 0.136 significant cohesive 12.40 0.117failure Example 3 6.08 0.139 some cohesive failure Example 4 14.50 0.040little cohesive failure Example 5 9.48 0.097 little cohesive failureExample 6 5.10 0.243 some cohesive failure Example 7 4.05 0.075 somecohesive failure Comparative 4.25 27.7 significant cohesive Example 1and some adhesive failure Comparative 3.59 1.650 slight cohesive,Example 2 some adhesive failure

Viscosity was measured using a Brookfield Model DV-II+ viscometer fittedwith a small volume sample adaptor and using a SCR-18 spindle at 45° C.and 50 rpm.

The electrical insulative properties were determined by coating andcuring the cathode material 130 on 23 micron thick nickel coated copperfoil. Resistance is measured using a Rigol model DM3068 multimeterconnected to a weighed custom-made fixture. The positive lead of themultimeter is connected to an upper pad which contacts the upper surfaceof the cathode layer and a negative lead which contacts the underside ofthe substrate. The gold plated contact pads are approximately onecentimeter in diameter. Direct current resistance is measured by placingthe cathode sample printed on the substrate between the upper and lowerplates of the test fixture. Thickness of the printed cathode layer ismeasured using a Mitutoyo Model ID-H0530E digital micrometer, thecathode layer thickness is determined by subtracting the measuredsubstrate thickness from the total thickness.

Adhesion of the cathode material 130 to the substrate was determined bytape tests. The cathode material 130 was coated onto a nickel-coatedcopper substrate and dried at 100° C. for 15 minutes. Using a standardball point pen, a score is made in the cathode layer from one corner ofthe solid printed area diagonally across to the opposite corner andlikewise with the other pair of corners forming an X pattern. A piece ofadhesive tape is adhered partially covering the cathode material 130 andpartially covering the uncoated nickel-coated copper substrate. The tapewas removed quickly at a 150 degree angle. The cathode layer is theninspected visually for the extent of adhesive failure between thecathode layer and the substrate and for cohesive failure within thecathode layer as indicated by cathode material 130 adhering to the testtape. The results of the tests are shown in Table 5.

Electrolyte Material

In a further embodiment, the electrolyte material 132 of the presentapplication includes a polymer, a salt, and a solvent. Ink jet printingtechnology may be utilized to apply the electrolyte material to asubstrate during the manufacture of a battery.

The electrolyte material provides a physical separation between theanode layer and the cathode layer, and allows diffusion transport of theionic salt from the anode to the cathode.

The electrolyte material may have flow characteristics to allow for theelectrolyte material to be properly jetted from the heads. Such flowcharacteristics may be defined by viscosity, surface tension, or fluidsolids content (NV). The viscosity may range from about 3.0 to 20.0 cP,preferably from about 3.0 cP to about 8.0 cP. The surface tension mayrange from about 30 dynes/cm to about 50 dynes/cm. The fluid solidscontent (NV) may range from about 0.5% to about 20.0%, preferably fromabout 1.0% to about 5.0%, and most preferably from about 1.0% to about2.0%. In some embodiments, the electrolyte material is jetted from theprint head at room temperature. In other embodiments, the print head maybe heated to about 25° C. to about 55° C., preferably about 43° C.

In one embodiment, the electrolyte material may include from about 0.5%to about 2.5%, preferably from about 1.0% to about 1.5%, by weight ofthe polymer; from about 0.5% to about 5.0%, preferably from about 2.0%to about 3.0%, by weight of the ionic salt; and from about 80.0% toabout 98.0%, preferably from about 95.0% to about 98.0%, by weight ofthe solvent.

Once the electrolyte material is applied to the substrate, a majority ofthe solvent is vaporized. Vaporization includes material changes to thegaseous state by active means such as heat or other similar processes aswell as by passive means such as evaporation or other similar processes.The substrate onto which the electrolyte material is jetted may bemaintained at an elevated temperature in the range from about 150° F. toabout 300° F., preferably at about 290° F., to promote vaporization ofthe solvent. The temperature of the print head and/or the substrate mayvary depending on the solvent.

The polymer suitable for use may be a polyimide, such as a terpolymerpoly(pyromellitic dianhydride+3,3′,5,5′-tetramethyl-4,4′-methylenedianiline/2,4,6-trimethyl-1,3-phenylenediamine])imide(poly(PDMA+TMMDA/DAMs)imide) by Solicore, Inc. (Lakeland, Fla.), andformed by reacting PMDA, 33.3 mole % DAMs and 66.7 mole % TMMDA. Anothersuitable polymer is a polyimide such as Matrimid 5218 by Huntsman (SaltLake City, Utah). Other suitable polymers include a functionalizedpolyvinylidene fluoride homopolymer such as Kynar ADS by Arkema Chemical(King of Prussia, Pa.), a polyvinylidene fluoride homopolymer such asKynar HSV 900 by Arkema Chemical (King of Prussia, Pa.), apolyvinylidene fluoride homopolymer such as Kynar 761 by Arkema Chemical(King of Prussia, Pa.), a polyvinylidene fluoride copolymer such asKynar 2751 by Arkema Chemical (King of Prussia, Pa.), a polyvinylidenefluoride homopolymer such as Fluor Solef 5130 by Solvay (Houston, Tex.),a polyvinylidene fluoride homopolymer such as KF by Kureha (New YorkCity, N.Y.), a VDF/TFE copolymer such as VT-475 by Daikin (Decatur,Ala.), a poly(vinylidene fluoride-tetrafluoroethylene-propylene) such asDyneon BRE-7131X by 3M (St. Paul, Minn.), a poly(vinylidene fluoride)such as D-1 by Targray (Montreal, Canada), polyamide-imides, such assuch as Torlon 4000T by Solvay (Houston, Tex.), to name a few. Mixturesof polymers may also be employed.

In one embodiment, the ionic salt may be lithium bistrifluoromethanesulfonimide (LiTFSI) such as HQ-115 by 3M (St. Paul,Minn.). Other suitable salts such as LiCl, LiBr, LiI, LiPF₆, LiClO₄,LiB(C₂O₄)₂, LiAsF₆, LiBF₄, LiN(SO₂CF₂CF₃)₂, or LiCF₃SO₃, may be used.

The solvent may be gamma butyrolactone (GBL), or, alternatively,N-methyl-pyrrolidone. Other suitable solvents include n-gammavalerolactone, N-methyl-2-pyrrolidinone, 3-methyl-oxazolidinone,tetramethylurea, dimethylsulfoxide, dimethylformamide,dimethylacetamide, methylethylketone, methyl isobutyl ketone, ethylenecarbonate, propylene carbonate, dimethylcarbonate, ethylmethylcarbonate,diethylcarbonate, dimethoxyethane, dimethoxymethane, diethoxyethane,tetrahydrofuran, 2-methyl-tetrahydrofuran, 1,3-dioxolane,4-methyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, acetonitrile,methylacetate, ethylacetate, methyl butyrate, ethyl butyrate or anypolar aprotic solvent and mixtures thereof. The evaporation rate of thesolvent may range from about 0.01 to about 0.2, preferably from about0.02 to about 0.1 at 25° C., based on the evaporation rate scale wheren-butyl acetate is 1.0 at 25° C.

Preferably, dynamic surface tension ranges from about 30 dynes/cm toabout 50 dynes/cm. Static surface tension ranges from about 30 dynes/cmto about 50 dynes/cm. Example surface tension modifiers are soluble inpolar aprotic solvents. Such surface tension modifiers include non-ionicsurfactants such as fluorosurfactants, alkyl pyrrolidinones, and thelike, and anionic, cationic, zwitterionic surfactants. Alternatively thesurface tension of the electrolyte material may be adjusted using aco-solvent with different surface tension than the primary solvent. Suchsolvents may include more volatile solvents of lower surface tensionsuch as low molecular weight alcohols, for example, methanol, ethanol,1-propanol, 2-propanol, 1-butanol, low molecular weight ethers, such asiso-propyl ether, low molecular weight amines such as iso-propyl amine,and low molecular weight aliphatic or aromatic compounds.

The layer of electrolyte material may be formed by multiple passes ofthe print head(s) in order to obtain the desired thickness. In someembodiments, the thickness may range from about 10 microns to about 30microns, preferably from about 16 microns to about 22 microns. Thisthickness may be obtained by making up to 50 passes, preferably up toabout 40 passes, and more preferably between about 20 passes and 30passes, of the printing unit over the substrate, although the number ofpasses is dependent on various factors such as, for example, selectionof the print head type, jetting performance, fluid solids content of theelectrolyte material, and mass flow rate.

The following examples further illustrate the disclosure but, of course,should not be construed as in any way limiting its scope. Three exampleelectrolyte materials useful in the present disclosure were prepared asfollows:

poly Viscosity Active GBL (PDMA + TMMDA/ (at 32° C./ Print head comp. (%by DAMs)imide LiTFSI 50 rpm) mass flow flow rate wt.) (% by wt.) (% bywt.) (cp) (mg/s) (mg/s) Example 1 93.46 2.18 4.36 10.5-10.9 26.2 1.71Example 2 96.73 1.09 2.18 4.32 94.1 3.08 Example 3 95.64 1.45 2.90 5.9177.5 3.38

To prepare the electrolyte material, the solvent was placed in a vesselon a magnetic stirrer. The magnetic stirrer was started prior to addingthe polymer. The polymer was sifted into the solvent in small incrementswith good agitation to prevent settling. Once the polymer is fullydissolved as indicated by a transparent solution, the ionic salt wasthen similarly sifted into the solvent to prevent settling.

Once the electrolyte material is thus prepared, it is filtered through a1.5 micron rated glass fiber syringe filter. After filtration theelectrolyte material is degassed under vacuum at about −27 inches ofmercury with stirring for about 30 minutes. The degassed electrolytematerial is then supplied to a Fujifilm Dimatix QS-80 printhead forevaluation of jetting performance, in particular the quality andconsistency of drop formation and the mass flow rate through the printhead. The print head is operated by firing all of the print head nozzlescontinuously at a frequency of 8.0 kHz. The electrolyte material supplyvessel is maintained at −2 inches of water vacuum. According to themanufacturer's literature, the preferred viscosity range for the DimatixQS-80 print head is between 8 and 20 cp. After printing and solventevaporation, the electrolyte material composition of Example 1 shownabove provides a satisfactory polymer membrane layer. However thejetting performance of Example 1 is problematic and is characterized byhighly inconsistent droplet ejection leading to diminished mass flowfrom the print head and mist generation over the substrate. The low massflow forces more passes over the substrate to dispose the requiredamount of polymer and lithium salt while the misting wastes material andmay compromise the performance of the nearby adhesive layer on thesubstrate.

Surprisingly, it was found that by diluting the composition of Example 1with additional solvent (in this case gamma butyrolactone) to aviscosity below the print head manufacturer's recommended range of 8 to20 cp, the drop ejection performance could be greatly improved. This isdescribed in Examples 2 and 3. As with example 1, a satisfactory polymermembrane layer is created with Examples 2 and 3.

More surprisingly even though the dilution lowered the concentration ofactive components in the electrolyte material composition (weightpercent sum of polymer and lithium salt) the drop ejection qualityimprovement lead to a greatly increased mass flow rate from the printhead thus lowering the number of passes to dispose the active componentson the substrate and improving efficiency. Further, Example 2 shows thateven though the mass flow rate from the print head is lower than Example1, the net active component flow rate is higher since it is higher inthe ink composition.

Jetting Application of Compositions

Referring to FIG. 16, a material 1210 may be jetted using a device 1200having a housing 1202 with a surface 1204. The jettable material 1210may include an adhesive material 128, an insulator material 144, acathode material 130, and/or an electrolyte material. The surface 1204has a plurality of jet nozzles 1206, 1208. In FIG. 3, two rows ofnozzles 1206, 1208 are shown, although the device 1200 can have one ormore rows of nozzles depending on the needed resolution. The housing1202 includes a chamber (not shown) in communication with the nozzles1206, 1208 and also in communication with a source 1210 of insulatormaterial 144 via a tube or other communication media 1212. The device1200 is controlled by a control device 1214 that may be any suitableprint controller well known to this skilled in the art.

During the manufacturing of the battery, the jettable material 1210 maybe jetted from a jet system containing a series of ink jet cartridges(e.g., bubble jet cartridges, thermal cartridges, piezoelectriccartridges, continuous ink jet systems, etc.). A bubble jet may emit adrop of liquid when excited by a heater. A piezoelectric system mayeject a drop of liquid when excited by a piezoelectric actuator. Thedrop is emitted from a tiny hole in the jet cartridges. The cartridgesmay contain any number of holes. Commonly, jet cartridges can be foundwith six hundred holes, often arranged in two rows of three hundred. Thejet units may be known print cartridge units such as those manufacturedby Hewlett Packard, Lexmark, Spectra, Canon, etc. An example of a jetcartridge and jet head is described in Murakami et al. U.S. Pat. No.7,240,998. Continuous systems are available from Kodak under the tradename Versamark.

The jet system or any of the jet systems as disclosed herein may be usedto emit the jettable material 1210 from the ink jet cartridge(s). Thejettable material 1210 may be jetted from one print head moving alongthe width of the substrate, or from multiple print heads jetting ontothe substrate in-line. The substrate may move continuously through theprint unit as the jettable material 1210 is jetted, or may remain staticduring jetting. The layer of jettable material 1210 may be formed bymultiple passes of the print head(s) in order to obtain the desiredthickness having sufficient adhesive strength.

Jetting performance is evaluated by drop size, nozzle wet-out, satelliteformation or tailing (described in greater detail below), mass flowrate, and frequency response. Mass flow rate refers to the consistencyof the flow through the nozzles over a period of time. The frequencyresponse refers to the consistency of the performance over a range ofspeeds.

The jet system may be used to “print” or jet the jettable material 1210having a shape onto the substrate. For example, a shape controller mayreceive shape data from a data system. The shape data may represent theshape to be printed. The shape data may include variable shape data thatchanges relatively frequently, semi-fixed shape data that changes lessfrequently, fixed shape data that remains static, and any combination ofvariable, semi-fixed, and fixed shape data. Some or all of the shapedata may be stored as binary data, bitmap data, page description code,or a combination of binary data, bitmap data, and page description code.For example, a page description language (PDL), such as PostScript orPrinter Command Language (PCL), may be used to define and interpretshape data in some embodiments. The data system may then electronicallycontrol jet system to print the shape represented by some or all of thedifferent types of shape data (or any portion thereof) onto thesubstrate. In some embodiments, a vacuum source or heat source may bepositioned next to or near jet system.

As is customary in the ink jet production art, any type of cleaningsystem may be utilized to clean the ink jet print heads.

Any of the systems or compositions described herein may be modified toallow formation of different drop sizes of the jettable material 1210.The drop size should be consistent to form a continuous, consistentlayer of the jettable material 1210.

Any of the systems described herein may be modified to allow formationof different drop sizes of the jettable material 1210. In general, ahigher resolution grid, that is a grid with 300 dpi or greater, alongwith matched drop size improves collection of the jettable material1210. Also, as the dpi of the grid increases, the size of the drops thatare most efficacious in general are smaller. A larger drop size is moresusceptible to forced wetting of areas to be imaged. This forced wettingcan cause a decrease in shape quality due to a reduction in printdensity. Such forced wetting can be minimized by the addition/removal ofone or more constituents and/or changing or adjusting one or morephysical properties of the jettable material 1210. For example, reducingcertain surfactants may reduce ghosting while utilizing, adding, and/orsubstituting other surfactants may also improve shape quality.

Properties of the jettable material 1210 and of the substrate may bevaried to achieve a desirable interaction between the shape that isprinted with the jet system and the substrate. In particular,manipulating the viscosity of the jettable material 1210 to about 1 toabout 30 cP (or mPa·s), in some embodiments preferably about 1 to about20 cP, prevents flooding, that is forced wetting that loses the image,including ragged edges and lines, as well as minimizes ghosting.Ghosting may occur when jettable material 1210 migrates to out of theshape. In some embodiments, it may be important that the viscosity ofthe adhesive material 128 be maintained at a value less than 30 cP, insome embodiments preferably less than 20 cP (or mPa·s) to allow for thejettable material 1210 to be emitted from a thermal jet head. Otherchemical and/or materials science properties might be utilized to reduceor eliminate this effect. The jettable material 1210 may also include athixotropic fluid that changes viscosity under pressure or agitation.Manipulating the surface tension of the jettable material 1210 can alsoreduce spreading.

Another process variable is the substrate itself. One or more coatingsmay be applied thereto to alter the interaction of the jettable material1210 with the substrate. In the case of other substrates, such as acircuit board, a plastic sheet, a film, a textile or other sheet, aplanar or curved surface of a wall, or other member, etc., the surfaceto which the jettable material 1210 is to be applied may be suitablyprepared, processed, treated, machined, textured, or otherwise modified,if necessary or desirable.

A still further option is to modulate/control the temperature of one ormore process parameters. For example, one might elevate the temperatureof the jettable material 1210 upon application thereof to the substrateto improve adherence and facilitate dispensing thereof. Alternatively,or in addition, the substrate may initially be heated during applicationof jettable material 1210 to control adhesion, drop shape/size, and thelike, and/or the substrate may be chilled at some point in the processonce the jettable material 1210 is applied thereto so that the viscosityof the jettable material 1210 is increased, thereby reducing spread ofthe jettable material 1210 into non-wetted areas.

One could further use multiple different liquids dispensed by separatejet devices that, when applied together, create a jettable material 1210that has improved adherence and/or viscosity and/or other desirablecharacteristic. The liquids may be applied at the different or sametemperatures, pressures, flow rates, etc.

The compositions, apparatuses, and methods disclosed herein are alsorelevant in other industries and other technologies, for example,textiles, pharmaceuticals, biomedical, and electronics, among others.For example, variably customizable adhesives having enhanced sealingproperties or water or fire resistance may be selectively applied towebs of textiles such as may be used to manufacture clothing or rugs,and/or may be used various types of applications such as in theproduction of radio frequency identification (“RFID”) tags on articles.Other industries may also benefit from selective application of anadhesive material 128 to a substrate.

It will be understood that the foregoing is only illustrative of theprinciples of the systems and methods disclosed herein, and that variousmodifications can be made by those skilled in the art without departingfrom the scope and spirit of such systems and methods. For example, theorder of some steps in the procedures that have been described are notcritical and can be changed if desired. Also, various steps may beperformed by various techniques.

Preferred embodiments of this disclosure are described herein, includingthe best mode known to the inventors for carrying out the disclosure.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the disclosure to be practicedotherwise than as specifically described herein. Accordingly, thisdisclosure includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the disclosure unlessotherwise indicated herein or otherwise clearly contradicted by context.

Lithium Material

In one embodiment, a lithium composition for the anode material 134 mayinclude metallic lithium particles and a solvent that may be extrudedonto a substrate during the manufacture of a battery.

In one embodiment, the anode material 134 is prepared in a separatesystem (hereinafter the “lithium system”) that is coordinated with thebattery system. The lithium system may include a printing unit and anextrusion die. Such extrusion process may allow for greater control overthe shape and thickness of the lithium anode as desired for a particularsize battery. Lithium is extremely reactive, and certain measures may beundertaken in order to minimize the possibility of fires.

The lithium composition may comprise metallic lithium particles such asStabilized Lithium Metal Powder by FMC Corp. (Philadelphia, Pa.), alithium powder coated with a hydrocarbon polymer or other similarmaterial. For example, the stable lithium metal powder may be formed byheating lithium metal powder in an inert atmosphere, for example, in thepresence of a non-combustible hydrocarbon oil, to form a molten lithiummetal. A variety of hydrocarbon oils may be used, such as mineral oil,petroleum, shale oils, paraffin oils, and the like. The molten lithiummay then be dispersed using high sheer or other equivalent forces toform uniform droplets or particles of the lithium metal, and tofacilitate the distribution of droplets or particles in the hydrocarbonoil while avoiding agglomeration. In other embodiments, other possiblecoatings include a wax, an organic coating such as mineral oil orpetroleum-based oil, and a phosphoric coating that results in a lithiumphosphate protective layer, among others. In one embodiment, the lithiumparticles are stabilized by a hydrocarbon polymer coating that ispreferably processed in order to activate the lithium. Additionally, itmay be desirable for the lithium particles to be substantially free ofother metals.

The solvent enables the composition to be malleable and/or fluid,preferably without damaging the coating of the lithium particles. Thesolvent may be hexane, heptane, xylene, toluene, or other similarsolvent. In some embodiments, at least a portion of the solvent may bevaporized and/or removed prior to activation of the lithium. The mixtureof the metallic lithium particles and the solvent may have a viscosityin the range from about 50 Pa·s to about 250 Pa·s, preferably from about150 Pa·s to about 175 Pa·s.

The substrate may be a film or sheet of polyethylene, or a metal such asaluminum or copper. In some circumstances, it may be desirable for thesubstrate to be a non-conductive film such as a polyethyleneterephthalate. In other circumstances, it may be preferred for thesubstrate to be a conductive material such as nickel-coated aluminum.When an aluminum substrate is used, a non-lithium coated surface of thealuminum substrate that contacts any active portion of the battery otherthan the anode itself (i.e., the cathode or electrolyte material) may becovered with an insulating material to prevent a battery short. Thelayers of battery components may be modified based on the selection ofanode substrate.

Prior to the extrusion of a lithium composition, a boundary may bejetted using an ink jet print head of the printing unit onto thesubstrate. The boundary disposed on the anode substrate may be aphysical barrier, such as an insulator material 144 or an adhesivematerial 128 having a sufficient thickness, or a thin oleophobic barrierthat physically repels the lithium composition, to prevent the flow orspread of the lithium composition. In some embodiments, the boundary isformed by a boundary material comprised of a polymer and a solvent. Thepolymer may be a linear copolyester, a poly(amide imide), a polyimide,or other suitable polymers, and combinations thereof. In someembodiments, at least a portion of the solvent may be vaporized.

Next, the lithium composition may be extruded from a micro-tip ormicro-dispensing extrusion die onto the substrate or an intermediatelayer of material atop the substrate. Multiple extrusion tips may bepositioned along the width of the web to extrude the lithium compositionin an in-line process. Alternatively, the extrusion may comprise asingle tip that makes multiple passes over a particular area or shapeoutlined by the boundary.

The coating of the lithium particles may then be processed and thelithium may be activated. In one method of activation, the stabilizingcoating may be displaced as the substrate travels through a calendaringsystem which allows the lithium particles to form a contiguous solidproviding electrical continuity. The calendaring process may beundertaken in a dry room environment to control humidity, or thepossibility of water exposure to the lithium.

In another method of activation, the stabilizing coating may be burnedoff during a flash fusion process, and the lithium particles may befused into a contiguous solid that allows for electrical continuity. Dueto the high reactivity of lithium, flash fusion may be undertaken in acontrolled environment to prevent exposure of the lithium to air, water,and other natural elements. The controlled environment may include anenclosure or container around the flash fusion area that is filled withArgon or another stabilizing gas.

Once the lithium has been activated, a die cutter may cut an individualanode from the web within the lithium system. The individual anode maythen be placed on top of the battery layers prior to the folding of thebattery within the battery system.

It will be understood that the foregoing is only illustrative of theprinciples of the systems and methods disclosed herein, and that variousmodifications can be made by those skilled in the art without departingfrom the scope and spirit of such systems and methods. For example, theorder of some steps in the procedures that have been described are notcritical and can be changed if desired. Also, various steps may beperformed by various techniques.

Preferred embodiments of this disclosure are described herein, includingthe best mode known to the inventors for carrying out the disclosure.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the disclosure to be practicedotherwise than as specifically described herein. Accordingly, thisdisclosure includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the disclosure unlessotherwise indicated herein or otherwise clearly contradicted by context.

INDUSTRIAL APPLICABILITY

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar references inthe context of describing the invention (especially in the context ofthe following claims) are to be construed to cover both the singular andthe plural, unless otherwise indicated herein or clearly contradicted bycontext. Recitation of ranges of values herein are merely intended toserve as a shorthand method of referring individually to each separatevalue falling within the range, unless otherwise indicated herein, andeach separate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the disclosure and does not pose alimitation on the scope of the disclosure unless otherwise claimed. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential to the practice of the disclosure.

Numerous modifications to the present disclosure will be apparent tothose skilled in the art in view of the foregoing description.Accordingly, this description is to be construed as illustrative onlyand is presented for the purpose of enabling those skilled in the art tomake and use the disclosure and to teach the best mode of carrying outsame.

We claim:
 1. An adhesive material comprising a vinyl polymer and asolvent that includes xylene and toluene, wherein the adhesive materialhas a viscosity in the range from about 1.0 cP to about 20.0 cP suchthat the adhesive material can be applied to a surface using an ink jetprint head.
 2. The adhesive material of claim 1, wherein the viscosityis in the range from about 1.0 cP to about 8.8 cP.
 3. The adhesivematerial of claim 1, wherein the vinyl polymer comprises a terpolymer ofethylene, vinyl acetate, and maleic anhydride.
 4. The adhesive materialof claim 1, wherein the vinyl polymer has an average number molecularweight in the range of from about 30,000 to about 40,000 g/mol.
 5. Theadhesive material of claim 1, wherein the adhesive material does notdegrade gamma butyrolactone and n-methyl-2-pyrrolidone.
 6. The adhesivematerial of claim 1, wherein the ratio by weight of toluene to xyleneranges from about 1.125:1 to about 1.222:1.
 7. The adhesive material ofclaim 1, further comprising a further polymer.
 8. The adhesive materialof claim 7, wherein the further polymer is a terpolymer of ethylene,ethyl acrylate, and maleic anhydride.
 9. The adhesive material of claim1, further comprising one of a surfactant, a further polymer, a levelingagent, an inorganic compound, an organic compound, dielectric particles,dielectric resins, and compounds having electrically insulativeproperties.
 10. The adhesive material of claim 1, wherein the surfacecomprises one of a substrate and an intermediate layer disposed atop thesubstrate.
 11. The adhesive material of claim 10, wherein the substratecomprises one of copper and aluminum.
 12. The adhesive material of claim10, wherein the intermediate layer comprises one of an insulatormaterial and a cathode material.
 13. The adhesive material of claim 10,wherein the surface includes a portion of a substrate and a portion ofan intermediate layer disposed on the substrate.
 14. The adhesivematerial of claim 1, further comprising a device for use in an ink jetprint operation comprising: a housing; a series of ejection nozzlesmounted within the housing, each ejection nozzle capable of ejecting adrop on demand; and a source of the adhesive material communicating withthe nozzles.
 15. An adhesive adapted to be applied using an ink jetprint head, comprising: from about 1% to about 8% by weight of a vinylpolymer; from about 1% to about 98% by weight of toluene; and from about1% to about 98% by weight of xylene; and up to about 1.5% by weight of asurfactant; wherein the adhesive has a viscosity such that the adhesivecan be jetted by the ink jet print head.
 16. The adhesive of claim 15,wherein the vinyl polymer is present in an amount from about 2% to about7% by weight; wherein the toluene is present in an amount ranging fromabout 30% to about 68% by weight; and wherein the xylene is present inan amount of about 30% to about 68% by weight.
 17. The adhesive of claim15, wherein the vinyl polymer is present in an amount from about 4% toabout 5% by weight; wherein the toluene is present in an amount rangingfrom about 45% to about 55% by weight; and wherein the xylene is presentin an amount ranging from about 40% to about 45% by weight.
 18. Theadhesive of claim 15, wherein the ratio by weight of toluene to xyleneranges from about 1.125:1 to about 1.222:1.
 19. The adhesive of claim15, further comprising a heat-resistant polymer.
 20. A method ofmanufacturing a battery using an ink jet print head comprising the stepsof: jetting an adhesive onto a surface, and wherein the adhesivematerial comprises a solvent and has a viscosity in the range from about1.0 cP to about 20.0 cP; and vaporizing a portion of the solvent. 21.The method of claim 20, wherein the adhesive material comprises a vinylpolymer and a solvent that includes xylene and toluene, and wherein theviscosity of the adhesive material is in the range from about 1.0 cP toabout 8.8 cP.
 22. The method of claim 20, wherein a majority of thesolvent is vaporized.
 23. The method of claim 20, wherein the surfacecomprises a metallic substrate.
 24. The method of claim 23, wherein thesubstrate is heated to promote evaporation of the solvent.
 25. Themethod of claim 24, wherein the substrate is heated to a temperature inthe range from about 23° C. to about 176° C.
 26. The method of claim 20,further comprising the step of laminating the battery at a temperatureof at least 135° C.
 27. The method of claim 20, wherein the adhesiveforms a layer having a thickness of from about 10 microns to about 12microns.
 28. The method of claim 20, wherein the adhesive is jetted byan ink jet print head, and wherein the step of jetting includes relativemovement of the ink jet print head over the surface to form a layerthereon.
 29. The method of claim 28, wherein the relative movementincludes up to 50 passes.
 30. The method of claim 29, wherein therelative movement includes up to about 30 passes.
 31. The method ofclaim 30, wherein the relative movement includes up to about 15 passes.